Inhibiting treatment



Patented Oct. 15, 1946 INHIBITING TREATBIENT George C. Ward and BurnardT. Pull, Cumberland, Md., assignors to Celanese Corporation of America,a corporation of Delaware No Drawing. Application January 14, 1943,Serial No. 472,410

24 Claims (Cl. 8-61) This invention relates to the treatment of dyedtextile materials and relates more particularly to the preparation ofdyed fabrics made of or containing yarns having a basis of celluloseacetate or other organic derivative of cellulose having colorationsthereon fast to acid fading.

An object of our invention is to provide a novel method of treatingcolored fabrics having a basis of'cellulose acetate or other organicderivative of cellulose yarns which have been dyed with colorsordinarily not fast to acid fumes to inhibit the fading of said coloredtextile materials when exposed to suchfumes.

Another object of our invention is to provide colored fabrics having abasis of cellulose acetate or other organic derivative of celluloseyarns, which colored fabrics are highly resistant to acid fading. p p

Other objects of our invention will appear from the following detaileddescription.

In the coloration of textile materials it is very desirable that thecolors produced on the materials be as fast as possible to light,washing, and to other agencies such as acid fumes. Many dyestuffs yieldon organic derivative of cellulose materials desirable shades which arefast to wash ing but these dyestuffs often suffer from a lack offastness to acid fumes. When fabrics to which these dyestuffs have beenapplied are exposed to acid fumes, for example, the products ofcombustion of coal, gas, etc., the color undergoes a change in shade.This change is usually referred to as acid fading. The change whichoccurs may be a'dulling of the brightness of the shade in someinstances, and in others there may be a definite change in color. Thisundesirable effect is frequently observed inthe case of manyanthraquinone dyestuffs which yield valuable blue colors on organicderivative of' cellulose materials. When fabrics dyed with these colorsare exposed to acid fumes the colors change from a pure blue shade toone having a reddish cast. On continued exposure to the acid fumes theblue color may even change to a pink color. Such changes naturallyrestrict the range of usefulness of thesedyestuffs and methodsof'increasing the resistance of these dyes to acid fading are of greatcommercial importance. I

W have'now discovered that the acid-fading characteristics of organicderivative of cellulose textile materials dyed with dyestuffs which areordinarily notfast to the action of acid fumes maybesubstantiallyiimproved if there is applied to said dyed materialsyaprimary, secondary or tertiary aliphatic hydroxy aminehaving at leastthree carbon atoms in at least one of the alkyl chains linked to theN-atom of said aliphatic amine. Examples of suitable aliphatic amineswhich may be employed in accordance with our invention are3-amino-4-heptanol, 3-diethanolamino-4+heptanol,3-amino-3-methyl-2-butanol, 2 -amino-2methyl-1:3-propane-diol,3-diethylamino-propane-diol and N-dibutylamino-ethanol. The applicationof these hydroxy amines to dyed organic derivative of cellulose fabricsrenders said fabrics highly resistant to the fading action of acidfumes. Due to this enhanced acid fading resistancewhich is imparted tothe 'dycd fabrics by our novel treatment, the fabrics are much moresatisfactory in service. They may be exposed to the concentrations ofacid fumes normally present in the air for relatively long periodswithout any observed effect on the color. Fabric or other textilematerials treated in accordance with our invention are highlysatisfactory in service and, consequently, are of greatly increasedcommercial value.

The aliphatic hydroxy amine acid fading inhibitors of our invention maybe applied to said dyed textile materials from aqueous or aqueousalcoholic solutions by immersing the textile material in the aqueous oraqueous-alcoholic solutions thereof, but preferably the solutions areapplied by padding operations.

The concentration of the aliphatic hydroxy amines in the aqueous oraqueous-alcoholic solutions from which they are applied may varydepending on the amount of the hydroxy amine it is desired to place onthe textile material. Satisfactory results may be obtained by havingpresent in the solutions from 0.5 to 10% by weight of the hydroxy amine.However, we have found that in such solutions a 2% concentration of thehydroxy amine yields optimum results with respect to inhibiting acidfading. The aqueousalcoholic solutions employed as the solvent maycomprise from 10 to by weight of alcohol but, preferably, the alcohol ispresent in such amount that it comprises about 35% by weight of thesolution employed. The use of aqueous-alcoholic solutions enables theacid-fading inhibiting aliphatic hydroxy amines to be applied to saidtextile materials more rapidly and at lower temperatures. Betterpenetration is obtained due to the slight swelling effect which the:alcohol exerts on the organic derivative of cellulose materials andincreased amounts of the hydroxy amines are soluble in theaqueous-alcoholic solutions.

7 The temperature at which the amine-containingsolutionsare applied tothe dyed textile material may vary. When the solution comprises anaqueous solution of the amine and is applied by immersing the textilematerial therein, the temperature at which the solution is maintainedmay be from 40 to 90 C. and the material may be held therein for from 5to 60 minutes to ensure that a suitable amount of the amine will beabsorbed by the textile material. When a padding operation is employedfor applying the aqueous amine solution, higher solution temperaturesmay be employed, for example temperatures of from 6.0 to 90 C. Usually,temperatures of about 85 C. are preferred for carrying outthe-paddingoperation. When aqueous-alcoholic solutions of the amines arepadded on the textile materials, lower temperatures such as to 40 .C ,i.e., about room temperature, are preferred.

Advantageously, certain cation-active agents may be applied to thetextile materials prior to or simultaneously with the application of theacid-fading inhibitors. These agents not only serve to improve theadherence .of the inhibitors to the textile materials but also renderthe treated textile .materials quite resistant to the deleteriouseffects of washing. As a result, fabrics which have been so treated maybe washed with little or no loss in their resistance to acid fading.'The cation-active agents employed in accordance with this invention areusually substituted quaternary ammonium compounds, for example, thequaternary ammonium .salts of fatty acid alkylamides, and are sold underthe trade names of Aero Catamine, Sapamine KW, Igapal W, Hyamine A andTrigamine. When applied prior to the application of the amine, themanner in .which the cationactive agents are placed on the textilematerials may comprise either. immersing the textile material in anaqueous or aqueous-alcoholic solution of the cation-active agent orpadding it with such solution. When applied simultaneously with theacid-fading inhibitor, the cationactive agent is added to the aqueous oraqueousalcoholic solution of the amine and the resulting solution maythen be applied as heretofore described. Relatively small amounts ofcationactive agents may be employed to obtain the desired results. Thus,for example, when the cation-active agent is applied in aqueoussolution, prior to'treatment with the amines, to the organic derivativeof cellulose textile materials, aqueous solutions containing from 0.2 to1% by weight of the cation-active agent aresatisfactory. Maintaining the.textile materials in the solution for from 5 to 60 minutes while saidsolution is at a temperature of 30 to 75% C. is sufiicient to. renderthe material highly resistant to washing after the acid fading inhibitoris applied. Where the cation-active agent is added to theamine-containing aqueous or aqueous-alcoholic solution and is applied tothe textile material simultaneously therewith, the cation-active agentmay be present in the solution in concentrations of from 0.1 to 2% byweight. Optimum results are achieved with the cation-active agentpresent in the solution in a concentration of about 0.2% by weight.

In order further to illustrate our invention but without being limitedthereto, the followin examples are given:

Example I ard acid fading test method. The unwashed sample undergoes nochange in shade after a 16 hour exposure and becomes only slightlyduller after a 40 hour exposure. The washed sample undergoes a slightchange toward red after a 1G hour exposure and becomes considerablyredder after a 40 hour exposure. The untreated fabric fades considerablyafter 16 hours exposure and fades completely to pink in 40 hours.

Example II A cellulose acetate fabric, dyed as in Example I, is immersedin an aqueous solution containing 0.2% by weight of Aero Catamine whichis at a temperature of 50 C. and is maintained therein for 45 minutes.After this treatment the fabric is entered into an aqueous bathcontaining 3% of 3-amino-4-heptanol maintained at50 C. and is heldtherein for 30 minutes. The treated fabric is then dried and a portionthereof is washed in 0.5% soap solution at 37 C. for 15 minutes. Afterdrying, the washed and unwashed treated fabric is exposed to acid fumesin the standard testing device. The washed and unwashed treated fabricsundergo no change in shade after 16 hours exposure to the acid fumes andonly a slight change in shade is observed after 40 hours exposure. Asindicated in Ex.- ample I, a dyed but untreated sample of fabric fadescompletely after 40 hours exposure.

Example III Cellulose acetate fabric, dyed as in Example I, is paddedwith an aqueous-alcoholic solution containing 34.8% by weight of ethylalcohol and 4.3% by weight of 3-diethanolamino-4-heptanol. The solutionis padded on the fabric at 20 C. After the padded fabric is dried, partof the treated fabric is washed in 0.5% soap solution at 37 C. for 15minutes. After drying both washed and unwashed samples of the treatedfabric are exposed to acid fumes. No change in shade takes place on 16hours exposure and the treated fabrics become only slightly redder after40 hours exposure.

Example IV Cellulose acetate fabric, dyed as in, Example I, is paddedwith an aqueous solution containing 2% of 3-amino-3-methyl-2-butanol,the solution being at C. during the padding. The padded fabric is driedand a part washed for 15 minutes at 37 C. in 0.5% soap solution. Driedsamples of both the washed and unwashed treated fabrics are exposed toacid fumes. No change is observed in the shade of the unwashed sampleafter lfi hours exposure but the washed sample becomes slightly redderin that period. After a 40 hour exposure the unwashedsample becomessliglliltly redder while the washed sample becomes pin While ourinvention has been described more particularly in connection with thetreatment of dyed textile materials having a basis of cellulose acetateto inhibit the tendency thereof toward fading when exposed to acidfumes, dyed textile materials having a basis of other organicderivatives or cellulose may be treated in like pionate and celluloseacetate-butyrate, and cellulose ethers such as ethyl cellulose andbenzyl cellulose.

It is to be understood that the foregoing detailed description is givenmerely'by way of illustration and that many variations may be madetherein without departing from the spirit of our invention.

Having described our invention, what we desire to secure by LettersPatent is:

1. Process for improving the fastness of colorations on dyed organicderivative of cellulose textile materials to acid fading, whichcomprises treating said dyed organic derivative of cellulose textilematerial with an aqueous-alcoholic solution of a member of the groupconsisting of primary, secondary and tertiary aliphatic hydroxymono-amines having at least three carbon atoms in at least one of thealkyl chains linked to the N-atom of said aliphatic hydroxy mono-amine.

2. Process for improving the fastness of colorations on dyed organicderivative of cellulose textile materials to acid fading, whichcomprises applying to said organic derivatives of cellulose textilematerial a cation-active agent and amember of the roupconsisting ofprimary, secondary and tertiary aliphatic hydroxymono-amines having atleast three carbon atoms in at least one of the alkyl chains linked tothe N-atom of said aliphatic hydroxy mono-amine.

3. Process forimproving the fastness of colorations on dyed celluloseacetate textile materials to acid fading, which comprises applying tosaid cellulose acetate textilemateriala cation-active.

agent and a member of the group consisting of primary; secondary andtertiary aliphatic hydroxy mono-amines having at least three carbonatoms in at least one of the alkyl chains linked to the N-atom ofsaidaliphatic hydroxy monoamine.

4. Process forimproving the 'fastness'ofcolorations on dyed organicderivative of cellulose texi tile materials to acid fading, whichcomprises treating said dyed organic derivative of cellulose textilematerial with an aqueous solution of a cation-active agent and thentreating said material with an aqueous solution of a member of the groupconsisting of primary, secondary and tertiary aliphatic hydroxymono-amines having at least three carbon atoms in at least one of thealkyl chains linkedto the N-atom of said aliphatic hydroxy mono-amine.

5. Process for improving the fastness of colorations on dyed organicderivative of cellulose textile materials to acid fading, whichcomprises treating said dyed organic derivative of cellulose textilematerial with an aqueous solution of a cation-active agent and thentreating said material with an aqueous-alcoholic solution of a member ofthe group consisting of primary, secondary and tertiary aliphatichydroxy mono-amines having at least 3 carbon atoms in at least one ofthe alkyl chains linked to the N -atom of the aliphatic hydroxymono-amine.

6. Process for improving the fastness of colorations on dyed celluloseacetate textile materials to acid fading, which comprises treating saiddyed cellulose acetate textile material with an aqueous solution of acation-active agent and then .N-atom of said aliphatic hydroxymono-amine.

7. Process for improving the fastness of colorations on dyed celluloseacetate textile materials a to acid fading, which comprises treatingsaiddyed cellulose acetate textile material with an aqueous solutioncontaining from 0.2 to, 1% by weight of a cation-active agent and thentreatingsaid material with an aqueous-alcoholic solution of a member ofthe group consisting of primary, secondary and tertiary aliphatichydroxy monoamines having at least 3 carbon atoms, in at least one ofthe alkyl chains linked to the N-atom of the aliphatic hydroxymono-amine 8. Process for improving the fastness of colorations on, dyedcellulose acetate textile materials to acid fading, which comprisestreating said dyed material with an aqueous solution containing from 0.2to 1% by Weight of a cation-active agent and then treating said materialwith an aqueous alcoholic solution containing 0.5 to 10% by weight of amember of the group consisting of primary, secondary and tertiaryaliphatic hydroxy mono-amines having at least 3 carbon atoms in at leastone of the alkyl chains linked to the N-atom of the aliphatic hydroxymono-amine. l l l l 9. Process for improving the fastness of colorationson dyed cellulose acetate textile materials toacid fading, whichcomprises treating the said dyed cellulose acetate textile materialwithsan s aqueous solution containing, from 0.2 to 1% by tion at atemperature of 10 to 40 weight of a cation-active agent and thentreating said material with an aqueous-alcoholicsolu- C. containing 0.5to 10% by weight of a member of the group consistingof primary,secondary and tertiary aliphatic hydroxy mono-amines having at least 3carbon atoms in at least one of the alkylchains linked to the N-atom ofthe aliphatic hydroxy mono-amine. a

10. Process for improving the fastness of colorations on dyed celluloseacetate textile mate rials to acid fading, which comprises treating thediethanblamino-4-heptano1.

said dyed cellulose acetate textile material with an aqueous solutioncontaining from 0.2 to 1% ing said material with an aqueous alcoholicsolution containing from 0.5 to 10% by weight of 3- 11. Process forimproving the fastness of colorations on dyed cellulose acetate textilematerials to acid fading, which comprises treating said dyed celluloseacetate textile material with an aqueousalcoholic solution comprising acation-active agent and a member of the group consisting of primary,secondary and tertiary aliphatic hydroxy mono-amines having at leastthree carbon atoms in at least one of the alkyl chains linked to theN-atom of said aliphatichydroxy mono-amine.

12. Process for improving the fastness of colorations on dyed celluloseacetate textile materials to acid fading, which comprises treating saiddyed cellulose acetate textile material with an aqueous-alcoholicsolution containing from 0.5 to 10% by weight of a member of the groupconsisting ofprimary, secondary and tertiary aliphatic hydroxymono-amines having at least taining from 0.5 to

13. Process for improving the fa'stness-of coloration-s ondyed celluloseacetate textile materials .to acid fading, which comprises treating saiddyed cellulose acetate textile material with an aqueous solutioncontaining from 0. '1 to2% of a cation-active agent and then treatingsaid material with an aqueous solutioncontaining from 0.5 to 10% by:weight of a'member of the :group consisting of primary, secondaryandtertiary aliphatic hydroxy mono-amines having at least three carbonatoms in atleast one of the alkyl chains linked to the N-atomof said:aliphatic hydroxy mono-amine.

14. Process for improving the .f-astness of colan aqueous-alcoholicsolution containing from 0.1 to 2% of a cation-active agent and thentreating :said material with an aqueous solution coniby weight of amember of thegroup consisting of-primary, secondaryand tertiaryaliphatic hydroxy mono-amines having at vleast three carbon atoms :in atleast one of the alkyl chains linked to the N-atom of said .ali-

,phatic'hydroxy mono-amine.

:15. Process for improving the 'fastness of colorations on dyedcellulose acetate textile materials to acid fading, which comprisestreating said dyed cellulose acetate textile material with vanaqueous-alcoholic solution at :a temperature of 10 to 40 C. containingfrom 0.5 to 10% by weight of a'member of the group consisting ofprimary, secondary and tertiary aliphatic .hydroxy monoamines havingcatleast three carbon atoms in at leastrone of the alkyl chains linked tothe N-atom ofsaid aliphatic hydroxy mono-amine.

16.Process of improving the fastness of colorations on dyed celluloseacetate textile materials to acid fading, which comprises paddingsaididyed celluloseacetate textile material 'with an aqueous-alcoholicsolution containing from 0.1 to 2% of a cation-active agentand from 0.5to 10% by weight of a member of the group consisting of primary,secondary and tertiary aliphatic hydroxy mono-amines having at leastthree carbon atoms in at least one of the-alkyl chains linked to theN-atom of said aliphatic 'hydroxy mono-amine.

17. Process for improving the .fastness of colorations on dyed celluloseacetate textile materials to acid fading, which comprises treating saiddyed cellulose acetate textile material with an aqueous-alcoholicsolution containing a cationactive agent and from 0:5 :to 10% lby'weightof '3-diethanolamino-4-'heptanol.

18. Process for improving the fastness of .colorations on dyed celluloseacetatetextile material-s to acid rading,:which comprises treating saiddyed cellulose acetate textile material with an aqueous-alcoholicsolution containing a cationactive agent and from 0.5 to 10% by weightof3-amino-4-heptanol.

'19.'Process for improving the fastness of colorations on dyed celluloseacetate textile materials to acid fa/ding, which comprises padding saiddyed cellulose acetate textile material with an aqueous-alcoholicsolution containing from 0.1 to 2% of a cation-active agent and from 0:5to 10% by weightof 3-diethanolamino-e heptanol.

20. Process for improvingthe fastness of colorations-on dyed celluloseacetate textile materials to acid fading, which comprises treating saiddyed cellulose acetate textile material with an aqueous solutioncontaining from 0.1 to 2% of a cation-active agent and then treatingsaid material with an aqueous solution containing from 0.5 to 10% byWeight of '3-diethanolamino-4- heptano'l.

'21. 'Dyed textile materials having a basis of an organic derivative ofcellulose which are resistant to acid fading, characterized by havingpresent thereon a cation-active agent and a member of the groupconsisting of primary, secondary and tertiary aliphatic hydroxymono-amines, having at least three carbon atoms in at least one of thealkyl chains linked to the'N-atom'of said aliphatic hydroxy mono-amine.

22. Dyed textile materials having a basis of cellulose acetate whichareresistant to acid fading, characterized by having present thereon acation-active agent and a member of the group consisting .of primary,secondary and tertiary aliphatic hydroxy mono-amines, having at leastthree carbon atoms in at least one of the alkyl chains linked to theN-atom of said aliphatic hydroxy mono-amine.

123. Dyed textile materials having a basis of cellulose acetate whichare resistant to acid fading, characterized by having present thereon acation-active agent and 3-diethanolamino-4- heptanol.

'24. Dyed textile materials having a basis of cellulose acetate whichare resistant to acid-fad- ,ing, characterized by having present thereona

